CN103060842B - A kind of method preparing electrodeposited cobalt under big flow - Google Patents
A kind of method preparing electrodeposited cobalt under big flow Download PDFInfo
- Publication number
- CN103060842B CN103060842B CN201210575750.2A CN201210575750A CN103060842B CN 103060842 B CN103060842 B CN 103060842B CN 201210575750 A CN201210575750 A CN 201210575750A CN 103060842 B CN103060842 B CN 103060842B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- liquid
- electrodeposition
- chlorine
- negative pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of method preparing electrodeposited cobalt under big flow. Existing electrodeposited cobalt production method current efficiency in the course of processing is not high, and the electrodeposition time is long, and the electrodeposited cobalt of production is all extremely difficult to requirement from purity or the response rate. The technical solution used in the present invention is: metallurgical production gained oil removing afterchlorinate cobalt liquor is raw material in a wet process, is diluted with pure water, makes the Co in cobalt chloride solution2+It is 30 ~ 100g/l, as liquid before electrodeposition; In the electrowinning plant closed, at 5 ~ 15m3/h��m2Big flow and condition of negative pressure under liquid before electrodeposition is carried out electrodeposition. The present invention, in the process of preparation electrodeposited cobalt, adopts high flow capacity can reduce cathodic polarization, and current efficiency is high, it is possible to reaching more than 95%, direct current consumption is low; Adopt high flow capacity, it is possible to take away chlorine and oxygen that anode produces in time, it is prevented that its oxidation cathode cobalt is to ensure product quality.
Description
Technical field
The present invention relates to the preparation of electrodeposited cobalt, a kind of method particularly preparing electrodeposited cobalt under big flow.
Background technology
Cobalt has the premium properties such as corrosion-resistant, fusing point is high, ferromagnetism, is the important source material of various special steel, heat-resisting alloy, corrosion-resisant alloy, magnetic alloy etc., is widely used in the fields such as Aero-Space, machine-building, battery. The cobalt that purity is higher is widely used in magnetic material, superalloy materials; Purity reaches the cobalt of more than 99.999% and can be used as the target of advanced electronic component.
The production method of cobalt is generally adopted the mode of electrodeposition, cobaltous sulfate or cobalt chloride solution electrodeposition obtain, and for cobalt chloride solution, the reaction principle in electrolytic deposition process is as follows:
Negative electrode: Co2++2e-=Co;
2H++2e-=H2;
Anode: 2Cl--2e-=Cl2;
Co2++30H--e-=Co00H+H20;
2H20-4e-=4H++02��
Existing electrodeposited cobalt production method current efficiency in the course of processing is not high, and the electrodeposition time is long, and the electrodeposited cobalt of production is all extremely difficult to requirement from purity or the response rate, specifically there are these problems following:
1. in electrolytic deposition process, there is concentration polarization, current efficiency is very low, and traditional electrolyte is typically in 60% ~ 80%.
2. traditional electrolyte process electrolyte electric current is less, is typically in 200 ~ 300A/m2, the electrodeposition time is longer.
3. can produce chlorine and a small amount of oxygen and water after anode discharge generation oxidation reaction to react the hypochlorous acid etc. generated and can aoxidize cathode cobalt, make oxygen-containing in electrodeposited cobalt product to wait impurity, reduce the purity of cobalt.
4. adopting uncovered open electrolytic cell, in electrolysis bath, cobalt liquor is directly exposed in air, and during operation, the foreign material such as the copper scale on contact rod, iron filings and dust can pollute electric effusion at any time, causes that electricity cobalt product quality is difficult to ensure.
5., in traditional method, the additive such as boric acid, saccharin sodium need to be added to ensure the quality of product to reach requirement, so likely the subsequent treatment operation of liquid after electrodeposition be caused secondary pollution.
6. traditional electrodeposition mode, the process range of solution is that 60 ~ more than 100g/l, below 60g/l are difficult to process.
Summary of the invention
The technical problem to be solved is the defect overcoming above-mentioned prior art to exist, it is provided that a kind of method preparing electrodeposited cobalt under big flow, and it is by improving flow quantity before electrodeposition, to reduce because near negative electrode, ion concentration reduces and the cathodic polarization phenomenon that causes; And when high flow capacity, the chlorine that anode produces can be taken away timely, in order to avoid it forms hypochlorous acid oxidization cathode cobalt in liquid before electrodeposition and affects the purity of electrodeposited cobalt.
For this, the present invention adopts the following technical scheme that: a kind of method preparing electrodeposited cobalt under big flow, and its step is as follows: metallurgical production gained oil removing afterchlorinate cobalt liquor is raw material in a wet process, is diluted with pure water, makes the Co in cobalt chloride solution2+It is 30 ~ 100g/l, as liquid before electrodeposition; In the electrowinning plant closed, at 5 ~ 15m3/h��m2Big flow (i.e. high flow capacity) under liquid before electrodeposition is carried out electrodeposition.
Further, the electrowinning plant of described closing includes the cobalt liquid circulating slot, enclosed type electrolytic tank, gas-liquid separator, chlorine collection device and the vacuum negative pressure device that are sequentially connected in series, the chlorine that enclosed type electrolytic tank Anodic precipitates out enters in gas-liquid separator together with liquid after electrodeposition, vacuum dechlorination is carried out by gas-liquid separator, obtain dechlorination cobalt liquid and chlorine, described dechlorination cobalt liquid returns to as liquid before electrodeposition in cobalt liquid circulating slot, as the Co of the cobalt liquid that cobalt liquid circulating slot flows out2+Returning directly to the extraction process during hydrometallurgy produces during lower than 30g/l, described chlorine enters vacuum negative pressure device through chlorine collection device.
Further, the cathode cobalt plate obtained after electrodeposition, after going out groove, stripping plate, washing and shear, obtain finished product cobalt sheet; From vacuum negative pressure device vacuum removal chlorine out after pure water, concentrated sulphuric acid dehydrate, in hydrochloric acid synthesizer, it is synthetically derived hydrogen chloride together with high-purity hydrogen, adopting absorbing pure water, obtain high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse.
Further, in electrolytic deposition process, before electrodeposition, the temperature of liquid controls at 30 ~ 50 DEG C, and bath voltage is 2.4 ~ 2.8V, and before electrodeposition, the pH value of liquid is 1.5 ~ 3.0.
Further, in electrolytic deposition process, the electrowinning plant of closing maintains negative pressure at 0.03 ~ 0.08MPa.
Further, electric current density during electrodeposition is 500 ~ 800A/m2��
Compared with the conventional method, the invention have the advantages that
1. in the process of preparation electrodeposited cobalt, adopting high flow capacity can reduce cathodic polarization, current efficiency is high, it is possible to reaching more than 95%, direct current consumption is low.
2. in the process of preparation electrodeposited cobalt, adopt high flow capacity, it is possible to take away chlorine and oxygen that anode produces in time, it is prevented that its oxidation cathode cobalt is to ensure product quality.
3. without adding any additive in electrolytic deposition process, advantageously ensure that the quality of product, process favourable simultaneously for the subsequent handling of liquid after electrodeposition, subsequent handling will not be caused secondary pollution.
4. adopt the present invention to prepare electric current density used by electrodeposited cobalt relatively big, be substantially shorter electrolysis time, adopt 800A/m2Electric current, can produce per hour electricity cobalt 0.83Kg/m2, it is 3-4 times of tradition electrodeposition mode.
5. in tail gas, purity of chlorine gas feeding is high, reaches more than 85%, and hydrogen content is low, less than 4%, can use it for safely the synthetically prepared of hydrochloric acid.
6. adopting the electrodeposition mode of the present invention, the process range of solution is wide, and the solution of 30 ~ 100g/l all can efficient electrodeposition.
7. adopt enclosed type electrolytic tank to carry out electrodeposition, and adopt vacuum dechlorination to process liquid after electrodeposition, it is to avoid the uncontrollable discharge of chlorine and free chlorine, can be effectively improved production operation environment, alleviate the anticorrosion pressure of production equipment, be conducive to the physical and mental health of operator.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Below in conjunction with specification drawings and specific embodiments, the invention will be further described.
Metallurgical production gained oil removing afterchlorinate cobalt liquor (Co in a wet process2+=100 ~ 160g/l) for raw material, diluted with pure water so that it is concentration controls at 30 ~ 100g/L, as liquid before electrodeposition. With 5 ~ 15m in enclosed type electrolytic tank3/h��m2High flow capacity liquid before electrodeposition is carried out electrodeposition, control electric current density is 500 ~ 800A/m2, electrolyte temperature is 30 ~ 50 DEG C. Its tank voltage is 2.4 ~ 2.8V, and electrodeposition solution ph is 1.5 ~ 3.0. Controlling internal system (including cobalt liquid circulating slot, enclosed type electrolytic tank, gas-liquid separator and chlorine collection device) negative pressure by vacuum negative pressure device in the process of electrolysis is 0.03 ~ 0.08MPa.
The electrowinning plant of described closing is made up of cobalt liquid circulating slot, enclosed type electrolytic tank, gas-liquid separator, chlorine collection device and the vacuum negative pressure device being sequentially connected in series, the chlorine that enclosed type electrolytic tank Anodic precipitates out enters in gas-liquid separator together with liquid after electrodeposition, vacuum dechlorination is carried out by gas-liquid separator, obtain dechlorination cobalt liquid and chlorine, described dechlorination cobalt liquid returns to as liquid before electrodeposition in cobalt liquid circulating slot, as the Co of the cobalt liquid that cobalt liquid circulating slot flows out2+Returning directly to the extraction process during hydrometallurgy produces during lower than 30g/l, described chlorine enters vacuum negative pressure device through chlorine collection device.
The cathode cobalt plate obtained after electrodeposition, obtains finished product cobalt sheet after going out groove, stripping plate, washing and shear; From vacuum negative pressure device vacuum removal chlorine out after pure water, concentrated sulphuric acid dehydrate, in hydrochloric acid synthesizer, it is synthetically derived hydrogen chloride together with high-purity hydrogen, adopting absorbing pure water, obtain high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse.
After once having tested, stop DC source, treat that chlorine removes complete stopping circulating pump, open electrolysis bath and take out cathode cobalt product. Finished product cobalt sheet is obtained after stripping plate, pickling, washing, hot wash and shear.
Embodiment 1
Adopt hydrometallurgy gained cobalt chloride solution (Co2+:95g/lCu2+:0.0051g/lFe2+: < 0.001g/lNi2+: < 0.001g/lCd2+: < 0.001g/lCr2+: < 0.001g/lZn2+: < 0.001g/lMg2+:0.0018g/lAl2+: < 0.001g/lCa2+:0.0020g/lMn2+: < 0.001g/l oil: 4.35g/lpH:2.5) as liquid before electrodeposition, carry out electrodeposition in enclosed type electrolytic tank. Coutroi velocity 10 ~ 14m3/h��m2Electric effusion is pumped in electrolysis bath, keep internal system 0.03 ~ 0.05MPa negative pressure with vacuum negative pressure device, when switching on power after negative regulation in groove, keep 800A/m2Electric current density carry out electrodeposition. In the process of electrodeposition, its temperature is 30 ~ 50 DEG C, tank voltage is 2.4 ~ 2.8V, the chlorine that electrolytic process Anodic produces enters in gas-liquid separator together with liquid after electrodeposition, gas-liquid separation is carried out by gas-liquid separator, described dechlorination cobalt liquid returns in cobalt liquid circulating slot as liquid before electrodeposition, the vacuum removal chlorine of gained is after pure water, concentrated sulphuric acid dehydrate, in graphite furnace, hydrogen chloride it is synthetically derived together with high-purity hydrogen, adopt absorbing pure water, obtaining high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse.Carry out after going out groove peeling off, pickling, washing, hot water wash, obtain electrodeposited cobalt product, claiming its Mass Calculation electricity effect is 95.58%, and its cobalt content accounts for 99.9802% after testing, meets Co9998 standard.
Embodiment 2
Adopt hydrometallurgy gained cobalt chloride solution (Co2+:100g/lCu2+: < 0.001g/lFe2+: < 0.001g/lNi2+: < 0.001g/lCd2+:0.0008g/lPb2+: < 0.001g/lZn2+:0.0059g/lMg2+:0.0018g/lCa2 +:0.0016g/lMn2+: 0.00058g/l oil: 4.72ph=2.3) as liquid before electrodeposition, carry out electrodeposition in enclosed type electrolytic tank. Coutroi velocity 10 ~ 14m3/h��m2Electric effusion is pumped in electrolysis bath, keep internal system 0.06 ~ 0.08MPa negative pressure with vacuum negative pressure device, keep 800A/m2Electric current density carry out electrodeposition. In the process of electrodeposition, its temperature is 30 ~ 50 DEG C, tank voltage is 2.4 ~ 2.8V, the chlorine that electrolytic process Anodic produces enters in gas-liquid separator together with liquid after electrodeposition, gas-liquid separation is carried out by gas-liquid separator, described dechlorination cobalt liquid returns in cobalt liquid circulating slot as liquid before electrodeposition, the vacuum removal chlorine of gained is after pure water, concentrated sulphuric acid dehydrate, in graphite furnace, hydrogen chloride it is synthetically derived together with high-purity hydrogen, adopt absorbing pure water, obtaining high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse. Carry out after going out groove peeling off, pickling, washing, hot water wash, obtain electrodeposited cobalt product, claiming its Mass Calculation electricity effect is 95.3%, and its cobalt content accounts for 99.9813% after testing, meets Co9998 standard.
Embodiment 3
Adopt hydrometallurgy gained cobalt chloride solution (Co2+:50g/lCu2+:0.0018g/lFe2+: < 0.001g/lNi2+: < 0.001g/lCd2+:0.0008g/lPb2+: < 0.001g/lZn2+:0.0059g/lMg2+:0.0018g/lCa2 +:0.0016g/lMn2+: 0.00058g/l oil: 4.72ph=2.3) as liquid before electrodeposition, carry out electrodeposition in enclosed type electrolytic tank. Coutroi velocity 8 ~ 10m3/h��m2Electric effusion is pumped in electrolysis bath, keep internal system 0.06 ~ 0.08MPa negative pressure with vacuum negative pressure device, keep 800A/m2Electric current density carry out electrodeposition. In the process of electrodeposition, its temperature is 30 ~ 50 DEG C, tank voltage is 2.4 ~ 2.8V, the chlorine that electrolytic process Anodic produces enters in gas-liquid separator together with liquid after electrodeposition, gas-liquid separation is carried out by gas-liquid separator, described dechlorination cobalt liquid returns in cobalt liquid circulating slot as liquid before electrodeposition, the vacuum removal chlorine of gained is after pure water, concentrated sulphuric acid dehydrate, in graphite furnace, hydrogen chloride it is synthetically derived together with high-purity hydrogen, adopt absorbing pure water, obtaining high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse. Carry out after going out groove peeling off, pickling, washing, hot water wash, obtain electrodeposited cobalt product, claiming its Mass Calculation electricity effect is 95.19%, and its cobalt content accounts for 99.9904% after testing, meets Co9998 standard.
Claims (1)
1. the method preparing electrodeposited cobalt under big flow, its step is as follows: metallurgical production gained oil removing afterchlorinate cobalt liquor is raw material in a wet process, is diluted with pure water, makes the Co in cobalt chloride solution2+It is 30 ~ 100g/l, as liquid before electrodeposition; In the electrowinning plant closed, at 5 ~ 15m3/h��m2Big flow and condition of negative pressure under liquid before electrodeposition is carried out electrodeposition;
The electrowinning plant of described closing includes the cobalt liquid circulating slot, enclosed type electrolytic tank, gas-liquid separator, chlorine collection device and the vacuum negative pressure device that are sequentially connected in series, the chlorine that enclosed type electrolytic tank Anodic precipitates out enters in gas-liquid separator together with liquid after electrodeposition, vacuum dechlorination is carried out by gas-liquid separator, obtain dechlorination cobalt liquid and chlorine, described dechlorination cobalt liquid returns to as liquid before electrodeposition in cobalt liquid circulating slot, as the Co of the cobalt liquid that cobalt liquid circulating slot flows out2+Returning directly to the extraction process during hydrometallurgy produces during lower than 30g/l, described chlorine enters vacuum negative pressure device through chlorine collection device;
The cathode cobalt plate obtained after electrodeposition, obtains finished product cobalt sheet after going out groove, stripping plate, washing and shear; From vacuum negative pressure device vacuum removal chlorine out after pure water, concentrated sulphuric acid dehydrate, in hydrochloric acid synthesizer, it is synthetically derived hydrogen chloride together with high-purity hydrogen, adopting absorbing pure water, obtain high purity hydrochloric acid, the high purity hydrochloric acid of generation returns to extraction process reuse;
In electrolytic deposition process, before electrodeposition, the temperature of liquid controls at 30 ~ 50 DEG C, and bath voltage is 2.4 ~ 2.8V, and before electrodeposition, the pH value of liquid is 1.5 ~ 3.0;
In electrolytic deposition process, the electrowinning plant of closing maintains negative pressure at 0.03 ~ 0.08MPa;
Electric current density during electrodeposition is 500 ~ 800A/m2��
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210575750.2A CN103060842B (en) | 2012-12-26 | 2012-12-26 | A kind of method preparing electrodeposited cobalt under big flow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210575750.2A CN103060842B (en) | 2012-12-26 | 2012-12-26 | A kind of method preparing electrodeposited cobalt under big flow |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103060842A CN103060842A (en) | 2013-04-24 |
| CN103060842B true CN103060842B (en) | 2016-06-08 |
Family
ID=48103727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210575750.2A Active CN103060842B (en) | 2012-12-26 | 2012-12-26 | A kind of method preparing electrodeposited cobalt under big flow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103060842B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105935779A (en) * | 2016-06-22 | 2016-09-14 | 荆门市格林美新材料有限公司 | Cobalt powder preparing method |
| CN105887137B (en) * | 2016-06-24 | 2018-04-06 | 有研亿金新材料有限公司 | One kind reduces the brittle method of electrolytic cobalt |
| CN106835194A (en) * | 2017-01-12 | 2017-06-13 | 江苏凯力克钴业股份有限公司 | A kind of cobalt chloride electrodeposition process |
| CN108950598B (en) * | 2018-07-13 | 2020-03-27 | 有研亿金新材料有限公司 | Preparation method of electrolytic cobalt with low gas content |
| CN112831802A (en) * | 2020-12-31 | 2021-05-25 | 格林美（江苏）钴业股份有限公司 | Production method of high-purity cobalt tablet with content of 99.999% |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063718A (en) * | 1992-01-14 | 1992-08-19 | 北京大学 | The method of separating beavy metal impurity system high-purity rare-earth |
| EP1613785A1 (en) * | 2003-04-11 | 2006-01-11 | BHP Billiton SSM Technology Pty Ltd. | Reductive ammoniacal leaching of nickel and cobalt bearing materials |
| CN101008089A (en) * | 2006-12-29 | 2007-08-01 | 金川集团有限公司 | Electrodeposit cobalt method for insoluble anode |
| CN102330111A (en) * | 2011-09-22 | 2012-01-25 | 浙江华友钴业股份有限公司 | Method for preparing electric deposited cobalt |
| CN102808194A (en) * | 2012-07-04 | 2012-12-05 | 嘉兴科菲冶金科技股份有限公司 | Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine |
-
2012
- 2012-12-26 CN CN201210575750.2A patent/CN103060842B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063718A (en) * | 1992-01-14 | 1992-08-19 | 北京大学 | The method of separating beavy metal impurity system high-purity rare-earth |
| EP1613785A1 (en) * | 2003-04-11 | 2006-01-11 | BHP Billiton SSM Technology Pty Ltd. | Reductive ammoniacal leaching of nickel and cobalt bearing materials |
| CN101008089A (en) * | 2006-12-29 | 2007-08-01 | 金川集团有限公司 | Electrodeposit cobalt method for insoluble anode |
| CN102330111A (en) * | 2011-09-22 | 2012-01-25 | 浙江华友钴业股份有限公司 | Method for preparing electric deposited cobalt |
| CN102808194A (en) * | 2012-07-04 | 2012-12-05 | 嘉兴科菲冶金科技股份有限公司 | Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103060842A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108470951B (en) | Method for recovering valuable metals in waste nickel-cobalt-manganese ternary lithium ion battery | |
| CN103014760B (en) | Production method of electrolytic manganese metal | |
| CN103060842B (en) | A kind of method preparing electrodeposited cobalt under big flow | |
| CN106544703A (en) | Perforation Copper Foil foil machine and its production technology | |
| CN105886767A (en) | Recycling method for copper indium gallium selenide (CIGS) waste | |
| CN107904613A (en) | Method for recycling nickel-cobalt valuable metal from nickel-cobalt-iron high-temperature alloy | |
| CN102586851A (en) | Electrolytic method for relieving and reducing tin sludge generated in tin plating solution | |
| CN103498169A (en) | Preparation method for reducing sulfur impurities in electrolytic nickel | |
| CN102268692B (en) | Method for producing cathode copper by directly electrolyzing spongy copper | |
| CN201793799U (en) | Device for relieving generation of tin sludge in tin-plating solution | |
| CN105177623A (en) | Method for recovering tin from copper-tin waste | |
| CN206052186U (en) | Perforation Copper Foil foil machine | |
| CN109179801B (en) | Treatment method of trivalent chromium electroplating waste liquid | |
| CN104532293B (en) | The method of purifying nickel and nickel purifying plant in chemical nickel plating waste solution | |
| CN111501064A (en) | Production method of 6N copper | |
| WO2021233300A1 (en) | Apparatus and method for preparing high-purity iron using consumable anode electrolytic deposition | |
| CN102051635B (en) | Method for producing metal cobalt by adopting high-current density sulfuric acid electrolyte | |
| CN115652374A (en) | Pulse rotational flow reinforced metal electrolysis device | |
| CN108677017A (en) | A kind of recovery method of copper indium gallium selenide waste material | |
| CA3212097A1 (en) | Iron conversion system and applications | |
| CN105937040A (en) | Process for reducing cathode zinc direct-current current unit loss in zinc wet method smelting for processing high mixed ore | |
| CN104562083B (en) | Zinc hydrometallurgical process capable of reducing acid-zinc ratio of electrolyte under different manganese ion conditions | |
| CN103046076B (en) | A kind of preparation method of electro deposited nickel | |
| Kumar et al. | Electrowinning of nickel in the processing of polymetallic sea nodules | |
| CN104911630A (en) | Low bath voltage zinc electrolysis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |